Nonsegregating granular detergent-bleach products and their preparation



3,161,597 NONSEGREGATING GRANULAR DETER- GENT-BLEACH PRODUCTS AND THEIR PREPARATION James H. Young, Lewiston, N.Y., assignor to E. L du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Nov. 14, 1961, Ser. No. 152,181 9 Claims. (Cl. 25299) This invention relates to cleaning and washing compositions having I chin roperties. More particularly, it relates to nonsegregating rgent-bleach compositions which contain borate perhydrate products, to the production of such compositions, and to certain borate perhydrate products which are especially useful in the production of such compositions.

Granular detergent-perborate cleaning and washing compositions, e.g. for home laundry uses, have been prepared by mechanically mixing preformed detergent granules and crystalline sodium perborate tetrahydrate whose formula is NaBO -H O -3H O (or NaBO -4H O). However, the resulting mixtures have been far from satisfactory because of their tendency toward particle separation or segregation during handling due to the differences in particle size and density of the components. This segregation problem has been particularly troublesome when using the usual spray dried detergents, the particle size of which is considerably greater than that of the usual commercial sodium perborate.

Suggestions have been made to increase the particle size of the perborate by granulation procedures, but such procedures are costly and do not entirely overcome segregation. Another suggestion for solving the segregation problem was to add the perborate to the detergent mix before spray drying. Still another proposal was to mix sodium perborate tetrahydrate crystals with hot detergent granules to effect melting of the perborate, and then cool the mixture to resolidify the perborate on the detergent granules. Such prior methods have not proved entirely satisfactory either because particle segregation was not sutficiently reduced or because of the tendency of sodium perborate to decompose at the elevated temperatures employed.

It is an object of the invention to provide an improved method of producing completely nonsegregating granular detergent compositions containing a borate perhydrate product uniformly distributed therethrough. A further object is to provide borate perhydrate solutions which are especially well suited for use in preparing such compositions. Other objects will be apparent from the following description and examples.

The objects of the invention are accomplished by adding to an agitated body of noncationic detergent granules an amount of an aqueous borate perhydrate solution such as will result in a mixture of moist crumb-like aggregates, which solution comprises 45 to 75%, preferably 50 to 60% by weight of water (based upon the solution weight) and 25 to 55% of a borate perhydrate solute of a composition corresponding to from 1 to 2 moles of H and and from 0.5 to 1 mole of alkali (calculated as M 0, where M stands for at least one cation of the group consisting of sodium, potassium and ammonium cations) per mole of B 0 When applied to a granular detergent in amounts sufiicient to supply active oxygen equal to from about 0.1 to 3%, based upon the final composition weight, the amount of water simultaneously supplied is generally insufficient to present any serious drying problem. In fact, the mixture, which initially is in the form of moist crumb-like aggregates, generally sets up in a few minutes under continued agitation to a dry-appearing, free-flowing granular product. Should supplemental drying be con- United States Patent 0 3,161,597 Patented Dec. 15, 1964 ice sidered necessary or desirable, drying during or after the mixing step can be readily and simply effected by means of a stream of dry air at ordinary or slightly elevated temperature.

The granular detergent-bleach compositions produced in accordance with the invention are stable and completely nonsegregating. All granules thereof are essentially uniform in their over-all chemical composition and their borate perhydrate component is an integral part of the granule structure. They can be readily prepared with substantially no loss of active oxygen. --The borate perhydrate solutions used to prepare the detergent-bleach compositions should generally contain from 1 to 2 moles of H 0 per mole of B 0 If the mole ratio of H O :B O is less than about 1:1, the solubility of the borate perhydrate will generally be too low to make application of the solution to detergents practical in view of the relatively large amount of water which would have to be simultaneously applied. If the ratio is substantially greater than 2:1, a substantial amount of the H 0 will be wasted. The preferred mole ratios range from l.22:1.

The mole ratio of alkali (M 0) to B 0 in the above solutions should from 0.5-1:1. If the ratio is substantially less than 0.5 :1, or substantially greater than 1:1, substantial loss of H 0 or active oxygen generally results, particularly if the solution is employed at elevated temperatures.

The borate perhydrate solutions employed in preparing the final detergent-bleach compositions can be made using boric acid (H BO tetraboric acid (B 8 0 or boric anhydride (B 0 as the source of all or part of the B 0 component. However, the most convenient source thereof is sodium tetraboggtg, ,which can be employed either as t e a y rous compound or in any of its hydrated forms, such as the decahydrate fla B Q LQH O (bor'a'xfmnd otas sium tetrab and pentaboratcsfmmfi ah massiumfijiftt can also be employed to supply all or part of the Ofco'mponent.

If a sodium, potassium or ammonium borate is the source of all or part of the required B 0 it will, of course, also supply part or all of the required alkali. Other suitable sources of alkali are sodium and potassium hydroxides and oxides, and aqueous and anhydrous ammonia. Sodium and potassium peroxides can also be used as sources of the alkali and of part of the required H 0 However, the H 0 will preferably be supplied in the form of an aqueous hydrogen peroxide solution containing, for example, from 35 to 90% H 0 by weight. If highly concentrated hydrogen peroxide solutions are used, it may be necessary to add further amounts of water in order that the water content of the borate perhydrate solution be within the range of 45 to by weight.

The usual perborates, such as ate tetrahydrate, are quite insoluble at ordinary temperatures and application of solutions thereof at such temperatures to preformed detergent granules is not practical because of the large amount of water which must be applied along with a relatively small amount of perborate. It has been found, however, that the solubilities of such perborates increase rapidly with temperature and that solutions thereof containing from 45 to 75% water and from 25 to 55% of the perborate, calculated as the anhydrous compound (e.g., 25 to 55% NaBO -H O sometimes called sodiu monohydrate) can be handled at temperatures of 40 to 55 C. without solute separation or excessive decomposition occurring and can be successfully and efiiciently applied at such temperatures to granular detergents without introducing excessive amounts of water to obtain nonsegregating granular detergent-per- EXAMlNEF-i borate compositions. If the perborate solution is to be made and used at once, a temperature as low as 40 C. can be used; but to insure against solute separation before application to the detergent, it is preferred that the solution be maintained at a somewhat higher temperature. Temperatures substantially above 55 C. should be avoided in order to avoid excessive losses of active oxygen.

The composition of perborate solutions will, of course, correspond to an M :B O mole ratio of 1:1. If that ratio is decreased to 0.511, the solubility of the borate perhydrate will be sufficiently high to permit the use of solutions containing not more than 75% water at room temperature without solute separation occurring. When the M ous o mole ratio is intermediate 0.5:1 and 1:1, with M being either Na, K or NH alone, somewhat elevated temperatures may be necessary to avoid solute precipitation, with increasingly higher temperatures being required as the mole ratio approaches 1:1. Accordingly, when using solutions containing to 55% by weight of a borate perhydrate solute of a composition corresponding to 1 to 2 moles of H 0 and between 0.5 and 1 mole of M 0 per mole of B 0 (when M is either Na, K or NH, alone), the solution should be maintained during handling at such a temperature as will prevent solute precipitation. However, temperatures above 55 C. will not be required or used.

It has been found that borate perhydrate products of compositions corresponding to 0.5 mole of Na O, 0.25 to 1 mole of NH and 1 to 2 moles of H 0 per mole of B 0 have surprisingly high solubilities and that solutions thereof containing 25 to 55% of the borate perhydrate solute can be stored for extended periods at room temperature without solute precipitation occurring. Thus, such sodium-ammonium perhydrate solutions containing 55% water have been stored at room temperature for 4 to 6 weeks without solute precipitation occurring, while corresponding solutions containing 75% water have remained essentially precipitate free at room temperature for 1 to 3 days.

The method of the invention can be used to prepare granular nonsegregating detergent-bleach compositions using any of the granular detergent materials heretofore known to be suitable for use in preparing granular detergent-perborate compositions. As is well known, the granular detergent material should be free of components which are incompatible with the borate perhydrate products and which if present would react with and consume the active oxygen of the latter. They should also not be excessively contaminated with impurities, such as heavy metal compounds, which catalyze the decomposition of peroxygen compounds.

The t r ent anules ma and usually will, contain in addition to the deiergent, one or more'afi'dlilv'e siibstgu fimalhzfleiggggnt compgpggL of the usual granular detergent compositions will generally cofisi'iiiif' about may be common soaps such as the sodium and potassium salts of higher fatty acids, e.g., those acids derived from tallow, lard, coconut oil and other animal and vegetable oils and fats and various synthetically produced fatty acids. All such soaps are anionic detergents. More generally, the detergents used will be noncationic synthetic detergents, i.e. anionic and nonionic synthetic detergents, because of their high solubility, resistance to preeipitation in hard water and their good detergent and other desirable properties. Such synthetic detergents are well known to be suitable for use in detergent-perborate compositions.

Suitable anionic synthetic detergents include the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 10 to 18 carbon atoms, such as sodium dodecylbenzene sulfonate; the higher alkyl sulfates, e.g., sodium oleyl and stearyl sulfates; the sodium and potassium fatty acid monoglyceride sulfates; acrylamide sulfonates; coconut fatty acid monoethanolamine amides; and the sodium and potassium salts of alkyl-phenol-ethylene oxide ether sulfates.

Suitable nonionic synthetic detergents include the condensates of ethylene oxide with alkylphenols, higher aliphatic alcohols or propyl amine-ethylenediamine reaction products.

The above anionic and nonionic synthetic detergents are intended merely to be illustrative of those usable for the present purpose. Others which are well known to be compatible with sodium perborate in granular detergentperborate compositions can also be used in preparing the present detergent-bleach compositions.

The granular detergent to which the borate perhydrate solution is applied in accordance with the invention will most generally be at room temperature. The solution may be applied at somewhat elevated temperatures, e.g., while the detergent is at a temperature up to but not higher than about C., although elevated temperatures generally offer no particular advantage over room temperatures.

The borate perhydrate solutions may be applied to the preformed granular detergent in accordance with the invention in a number of ways. One method is to add the solution dropwise to an agitated body of the granular detergent until the latter is converted to a mixture of moist crumb-like aggregates. Severe agitation or crushing should be avoided, particularly when the granular shape and size of the original detergent granules are to be more or less retained. A rise in temperature, e.g., from room temperature to a maximum of about 40 C., usually occurs, probably due to heat of separation of the borate perhydrate solute from solution. The initial moist crumb-like or curdy mixture usually sets up within a few minutes to a dry-appearing, free-flowing granular product. If supplemental drying is necessary or desirable, this can be effected during or after the mixing by means of a stream of dry air at ordinary or somewhat elevated temperatures. No supplemental drying was necessary in preparing the detergent-bleach compositions of Examples 5 and 6 below. Substantially no active oxygen is lost during the mixing and/or drying operations. The amount of free water, i.e., water other than that bound as H 0 or present as water of hydration, in the final detergentbleach composition should not generally exceed about 6% of the weight of the composition.

The borate perhydrate solution can also be applied in finely divided form to an agitated body of granular detergent. Such finely divided form may be obtained by passing the solution through spray nozzles or by feeding it to a spinning disc. Agitation of the detergent granules may be effected by the use of simple well-known stirring or tumble-mixing devices. The Patterson-Kelly Twin Shell Liquid-Solids Blender is a tumble-mixer which is well suited for effecting rapid and uniform distribution ,thelike. Y" of the borate perhydrate solution on the detergent The detergent components of detergent granules 75 granules.

additive materials. Cam kalinef rrrafiz'riais sugg alkali metal carbonates, borates and silicafesl andthe triand dialkali metal orthol phosphates; neutral salts such as sodium sulfate; complexing or chelating agents, such as the alkali metal condensed v (i.e., molecularly dehydrate) phosphates, such as sodium pyrophosphate, metaphosphate and tripolyphosphate (Na P O and organic chelating agents such as the aminopolycarboxylic acids, e.g., ethgdmeia gifiiggg e w a mtt at as stisastmaamiacetic acid and their alkali ifiietjajlfsalts; soil suspending agents, such as cai'boxymethylcellulose and polyacrylates;

and coloring agents, g alm sn grjgh gfi ew soluble abrasive agents such as' ipowdered silica may also be included if the composition is intended for cleaning enamel surfaces pooking utensils The invention is illustrated by the following examples. All composition percentages in the examples and elsewhere are by weight.

Example 1 Thirty-eight (38) grams of CP. borax (Na B O was added with agitation to 39.6 g. (35 ml.) of 35% H (an aqueous solution of hydrogen peroxide containing 35% H 0 by weight). The reaction was endothermic and the volume of the resulting solution was 58 m1. Analyses showed that substantially no loss of active oxygen occurred during mixing. The mole ratios of H O :Na 0:B O in the resulting solution were 2:0.5z1, and the water content was 56%. A sample diluted with water to an active oxygen content of 1% had a pH of 8.3. Similar solutions were similarly prepared in which the mole ratio of H O :B O was varied from 1:1 to 2:1.

The above borate perhydrate solutions in which the mole ratio of Na O:B O is 0.5:l are somewhat viscous liquids which do not separate solute readily. They can be readily poured or sprayed at 25 to 30 C. and can be applied at those temperatures to granular detergents. When dried, they form water-free glasses. Samples of such solutions having a water content of 55% have remained precipitate-free for 4 to 6 weeks at room temperature; however, if diluted to a water content of 80%, solute separation occurred within about one week.

Since bleaching by the borate perhydrate product is facilitated by conditions of substantial alkalinity, i.e., a pH of at least about 9, it is preferred that the compositions of the borate perhydrate solutions employed correspond to M O:B O mole ratios greater than the 0.521 ratio of the solutions of Example 1. Solutions having M O:B O mole ratios ranging from about 0.63 to 1:1 are preferred since such solutions, when diluted to an active oxygen concentration of 1% give pH values of from about 9 to 10.2. The most preferred solutions of this type are those in which the alkali requirements are satisfied by both sodium and ammonium hydroxide and correspond to 0.5 mole of Na O and 0.25 to 1 mole of NH per mole of B 0 Illustrative of the preferred sodium-ammonium borate ring if maintained at a somewhat elevated temperature, the solution having an Na 0:B O mole ratio of 1:1 (Exp. No. l) requiring a temperature of 40 to 55 C.

Amounts Used tg.) Moles/Mole of B30: Exp. No

Borax 35% H20! NaOH Hi0: NarO Small amounts of sodium stannate stabilizer were incorporated in the above solutions during their preparation. The solutions had a specific gravity of about 1.3 and an active oxygen content of about 6.8%

Example 4 It is important that the borate perhydrate solution and the detergent-bleach composition prepared therefrom be stable respecting their active oxygen content. The stability of the borate perhydrate solution will gen erally be satisfactory if it is made from raw materials which are essentially free of peroxide decomposition catalysts. The commercially available 35 to 90% solutions of hydrogen peroxide are usually sufliciently free of such catalysts to permit their direct use, as are also the purer available grades of sodium, potassium and ammonium hydroxides. Some commercially available borax products are sufiiciently contaminated by peroxide decomposition catalysts as to make it desirable that they be purified before use and/ or that an effective peroxygen compound stabilizer be added to the perhydrate solution. These observations will be apparent from the typical stability test results reported below for various stabilized and unstabilized borate perhydrate solutions. In carrying out the test, a sample of the original perhydrate solution containing about 50 to 60% water was diluted to an active oxygen content of 1%, the diluted solution was heated under reflux at 60 C. for the time indicated in a clean, passive glass container, after which the solution was analyzed for its active oxygen content and the active oxygen loss was calculated. All stabilizer percentages reported are based on the weight of the perhydrate u I I r I perhydrate solutions are those shown in the following solutionexample:

Moles/Mole Example 2 Exp. 0115,0 Stabilizer, Hours Act. 0 Borate perhydrate solutions were prepared by mixing percent if i borax, 35% H 0 and concentrated ammonium hydroxide B10: w (28% NH;,) in the proportions shown by the following tabulation: 1 2 0.5 None 1 13.1 2 0.5 None 1 15.3 a taste l 22-1 1 Amounts Used (g.) Moles/Mole of B10; 2 o. 5 0 osDTPA. 1 01 2 z ma a- 2 a:

311115 a 3%, .9 31 3 N820 8 2 0.5 None 1 0.1

I Diethylenetriarnine pentaacetic acid. 3% 2:? Q 3:2 Sodium stannate,NazSnO;-3H:O. 95 97 2 05 (L25 60 Prepurified borax was used inmakmg the borate perhydrate solution. 33 22;? 3 312 31;: Samples of commercial sodium perborate tetrahydrate 481 ass 62.0 1.6 0.5 0. 41 from two different sources were used to prepare solutions at 60 C. which contained 1% active oxygen. When Substantially no loss of active oxygen occurred during mixing and the water contents of the resulting solutions ranged from about to 58%. Solutions such as those of Examples Nos. 1, 3, and 5 have remained precipitatefree upon standing 30 days at room temperature.

Example 3 Sodium borate perhydrate solutions having Na O:B O mole ratios greater than 0.5 :1 were prepared by mixing borax, 35 H 0 and sodium hydroxide in the proportions shown in the following tabulation. They can be handled satisfactorily without solute precipitation occurheated for 1 hr. at 60 C., one solution lost 6.5% of its active oxygen while the other lost 24.2%. Thus, solutions 3 to 8 of the above tabulation were substantially more stable than were the solutions prepared from commercial sodium perborate tetrahydrate.

The borax used to prepare the borate perhydrate solution of Exp. No. 8 of the above tabulation was the same as that used in Exp. Nos. 1-7, except that it had been purified before use. Purification was effected by dissolving 250 g. of the original commercial borax in 500 ml. of distilled water which contained 0.5 g. of diethylenetriamine tetraacetic acid (DTPA) and 5 g.

Na P- O -H O (C.P. crystals). Solution was effected by heating to boiling and, after filtering, the solution was cooled to C. The precipitated crystals were filtered off and washed 3 times with distilled water containing 0.17% of DTPA. Analyses showed the crystals to be essentially Na B O -10H O.

It is generally preferred that the borate perhydrate solution employed in making the granular detergentbleach composition be one which shows an active oxygen loss of not more than 1% per hour when subjected to 10 the 60 C. stability test described above. As shown by the stability data tabulated above, solutions exhibiting such stability can be effectively obtained by employing raw materials of sufiicient purity or by the addition of stabilizers such as DTPA or sodium stannate. Another 15 effective stabilizer is sodium silicate which is conveniently added as a solution containing 65% H 0, SiO and 10% Na O. Even though high purity raw materials are employed in preparing the borate perhydrate solution, the addition of an effective stabilizer is nevergo theless generally advisable. This is because of the possibility of the solution, subsequent to its preparation, becoming inadvertently contaminated with decomposition catalysts, and because the detergent material to which the solution is to be applied may contain such catalytic 25 materials in objectionable amounts.

Example 5 Completely nonsegregating detergent-bleach compositions were prepared by adding borate perhydrate solut-ions of the compositions shown in the following tabulation to agitated bodies of six commercial granular detergents sold under different brand names in grocery stores. Because the compositions of the first five of the detergents used are not known to applicant, they are indicated in the tabulation simply by the letters A, B, C, D, and E.

of 80% for 24 hours, after which the sample was analyzed to determine the active oxygen lost. For comparison, samples of three lots of a commercial detergentsodium perborate tetrahydrate product containing about 0.5% active oxygen were subjected to the same test. The results are tabulated below.

It will be seen from the above data that the detergentbleach compositions of Exp. Nos. l-6 were substantially more stable than was the commercial product.

Example 6 Detergent-bleach compositions containing about 0.5% active oxygen were prepared as indicated generally in Example 5 employing commercial granular detergents A, B, and F of Example 5 and one designated G, all as purchased in a grocery store. The resulting dry-appearing, free-flowing and nonsegregating mixtures were then stored for extended periods of time at room (ambient) conditions, following which they were analyzed and their active oxygen losses per month calculated.

Perhydrate Solution Used Deter- Time of Act. 0 Exp. No. Moles/Mole of B10; gent Storage, Loss/Mo.,

H7O, Stnbi- Mos. percent percent lizcr H O; N820 NH3 I None Nora-Stabilizer percentages are based upon the weight of the perhydrate solutioni The perhydrate solution of Exp. No. borax was used in all other experiments; however 1 was prepared using C.P. commercia.

in Exp. Nos. 3, 4, 7, 8 and 10, it was tax. A

purified prior to use as was the borax employed in Exp. N0. 8 of Example 4.

The composition of the sixth detergent, F, was approximately 50% sodium tripolyphosphate, Na P 0 17.5% of a mixture of sodium dodecylbenzene sulfonate and the sodium sulfates of fatty alcohols containing 12 to 14 carbon atoms, 13.9% sodium sulfate, 7.7% sodium silicate, and about 8% retained water with the balance consisting of materials such as coconut oil amide, carboxymethylcellulose and optical brightener. In each instance, the borate perhydrate solution was applied in an amount to provide a detergent-bleach composition containing about 0.4 to 0.6% active oxygen. The final dry-appearing, free-flowing and nonsegregating detergent-bleach compositions were then subjected to an accelerated stability test. This test involved exposing a 2 gram sample Samples of three separate lots of a commercial detergent-sodium perborate tetrahydrate product showed active oxygen losses of 6.1, 4.5 and 5.1% per month when stored for two months at room temperature.

Example 7 of the product to air at 60 C. and a relative humidity they were not crystalline like sodium perborate tetrahy- 9 drate, but were glassy, with no definite crystalline pattern. When dissolved in water to give a solution containing 1% active oxygen, the product having an H O :B O mole ratio of 1.3:1 gave a solution having a pH of 8.3-8.4. Sodium perborate solutions have a pH of 10.1-10.2.

A sodium-ammonium borate perhydrate solution containing 50.7% water and having a solute composition corresponding to 0.5 mole Na O, 0.5 mole NH, and 1.3 mole H per mole B 0 was prepared. Upon evaporation as indicated above, this solution yielded a dry glassy product which analyses indicated to be of a composition corresponding to the formula A solution thereof at a concentration to give 1% active oxygen had a pH of 9.1.

The borate perhydrate solutions, particularly the sodium-ammonium borate perhydrate solutions, described herein are well suited for use in preparing granular detergent-bleach compositions which are stable and completely nonsegregating.

I claim:

1. The method of producing a granular, nonsegregating detergent-bleach product comprising adding to an agitated body of material consisting essentially of granules of a detergent, a borate perhydrate solution in an amount such as will result in the formation of a mixture of moist crumb-like aggregates and will provide in said product an active oxygen content of from 0.1 to 3% based upon the product weight, said addition being made while each of said body of material and said solution is at a temperature of from room temperature to 55 C., and continuing the agitation of said mixture until a dry-appearing freefiowing product is obtained; said detergent being from the group consisting of (a) the sodium and potassium alkylbenzene sulfonates in which the alkyl groups contain .from to 18 carbon atoms and (b) the sodium and potassium sulfates of fatty alcohols containing 12 to 14 carbon atoms; said solution consisting essentially of 45 to 75% by weight of water and 25 to 55% by weight of a borate perhydrate solute consisting essentially of from 1 to 2 moles of H 0 and 0.5 to 1 mole of alkali per mole of B 0 said alkali being calculated as M 0 in which M represents at least one cation of the group consisting of sodium, potassium and ammonium.

2. The method of claim 1 wherein the borate perhydrate solute consists essentially of from 1 to 2 moles 10 of H 0 0.5 mole Na o, and from 0.25 to 1 mole of NI-I per mole of B 0 3. The method of claim 1 wherein the detergent is sodium dodecylbenzene sulfonate.

4. The method of claim 2 wherein the detergent is sodium dodecylbenzene sulfonate.

5. A granular, nonsegregating detergent-bleach product whose granules are uniform in their over-all chemical composition with each granule consisting essentially of a granule of a detergent having a borate perhydrate component as an integral part of the granule structure; said borate perhydrate being present in an amount to provide active oxygen equal to 0.1 to 3% based upon the weight of said product, and said borate perhydrate being a sodium-ammonium borate perhydrate consisting essentially of from 1 to 2 moles of H 0 0.5 mole of N2 0 and from 0.25 to 1 mole of NH per mole of B 0 and said detergent being from the group consisting of (a) the sodium and potassium alkylbenzene sulfonates in which the alkyl groups contain .from 10 to 18 carbon atoms and (b) the sodium and potassium sulfates of fatty alcohols containing 12 to 14 carbon atoms.

6. A detergent-bleach product according to claim 5 wherein the detergent is sodium dodecylbenzene sulfonate.

7. A solid sodium-ammonium borate perhydrate consisting essentially of from 1 to 2 moles of H 0 0.5 mole of Na O and from 0.25 to 1 mole of NH per mole of B203.

8. A product consisting essentially of an aqueous solution of a sodium-ammonium borate perhydrate consisting essentially of from 1 to 2 moles of H 0 0.5 mole of Na O and 0.25 to 1 mole of NH; per mole of B 0 9. A sodium-ammonium borate perhydrate of the formula:

References Cited in the tile of this patent UNITED STATES PATENTS 1,929,121 Seng Oct. 3, 1933 2,491,789 Young Dec. 20, 1949 2,706,178 Young Apr. 12, 1955 2,863,835 Goldsmith et a1. Dec. 9, 1958 2,937,998 Habernickel May 24, 1960 FOREIGN PATENTS 838,667 Great Britain June 22, 1960 

1. THE METHOD OF PRODUCING A GRANULAR, NONSEGREGATING DETERGENT-BLEACH PRODUCT COMPRISING ADDING TO AN AGITATED BODY OF MATERIAL CONSISTING ESSENTIALLY OF GRANULES OF A DETERGENT, A BORATE PERHYDRATE SOLUTION IN AN AMOUNT SUCH AS WILL RESULT IN THE FORMATION OF A MIXTURE OF MOIST CRUMB-LIKE AGGREGATES AND WILL PROVIDE IN SAID PRODUCT AN ACTIVE OXYGEN CONTENT OF FROM 0.1 TO 3% BASED UPON THE PRODUCT WEIGHT, SAID ADDITION BEING MADE WHILE EACH OF SAID BODY OF MATERIAL AND SAID SOLUTION IS AT A TEMPERATURE OF FROM ROOM TEMPERATURE TO 55*C.,AND CONTINUING THE AGITATION OF SAID MIXTURE UNTIL A DRY-APPEARING FREEFLOWING PRODUCT IS OBTAINED; SAID DETERGENT BEING FROM THE GROUP CONSISTING OF (A) THE SODIUM AND POTASSIUM ALKYLBENZENE SULFONATES IN WHICH THE ALKYL GROUPS CONTAIN FROM 10 TO 18 CARBON ATOMS AND (B) THE SODIUM AND POTASSIUM SULFATES OF FATTY ALCOHOLS CONTAINING 12 TO 14 CARBON ATOMS; SAID SOLUTION CONSISTING ESSENTIALLY OF 45 TO 75% BY WEIGHT OF WATER AND 25 TO 55% BY WEIGHT OF A BORATE PERHYDRATE SOLUTE CONSISTING ESSENTIALLY OF FROM 1 TO 2 MOLES OF H2O2 AND 0.5 TO 1 MOLE OF B2O3, SAID ALKALI BEING CALCULATED AS M2O IN WHICH M REPRESENTS AT LEAST ONE CATION OF THE GROUP CONSISTING OF SODIUM, POTASSIUM AND AMMONIUM.
 5. A GRANULAR, NONSEGREGATING DETERGENT-BLEACH PRODUCT WHOSE GRANULES ARE UNIFORM IN THEIR OVER-ALL CHEMICAL COMPOSITION WITH EACH GRANULE CONSISTING ESSENTIALLY OF A GRANULE OF A DETERGENT HAVING A BORATE PERHYDRATE COMPONENT AS AN INTERGRAL PART OF THE GRANULE STRUCTUREF SAID BORATE PERHYDRATE BEING PRESENT IN AN AMOUNT TO PROVIDE ACTIVE OXYGEN EQUAL TO 0.1 TO 3% BASED UPON THE WEIGHT OF SAID PRODUCT, AND SAID BORATE PERHYDRATE BEING A SODIUM-AMMONIUM BORATE PERHYDRATE CONSISTING ESSENTIALLY OF FROM 1 TO 2 MOLES OF H202, 0.5 MOLE OF JA2O AND FROM 0.25 TO 1 MOLE OF NH3 PER MOLE OF B2O3F AND SAID DETERGENT BEING FROM THE GROUP CONSISTING OF (A) THE SODIUM AND POTASSIUM ALKYLBENZENE SULFONATES IN WHICH THE ALKYL GROUPS CONTAIN FROM 10 TO 18 CARBON ATOMS AND (B) THE SODIUM AND POTASSIUM SULFATES OF FATTY ALCOHOLS CONTAINING 12 TO 14 CARBON ATOMS. 